Femtosecond Photon-Mediated Plasma Enhances Photosynthesis of Plasmonic Nanostructures and Their SERS Applications

Laser ablation in liquid has proven to be a universal and green method to synthesize nanocrystals and fabricate functional nanostructures. This study demonstrates the superiority of femtosecond laser-mediated plasma in enhancing photoredox of metal cations for controllable fabrication of plasmonic nanostructures in liquid. Through employing upstream high energetic plasma during laser-induced microexplosions, single/three-electron photoreduction of metallic cations can readily occur without chemical reductants or capping agents. Experimental evidences demonstrate that this process exhibits higher photon utilization efficiency in yield of colloidal metal nanoparticles than direct irradiation of metallic precursors. Photogenerated hydrated electrons derived from strong ionization of silicon and water are responsible for this enhanced consequences. Furthermore, these metallic nanoparticles are accessible to self-assemble into nanoplates for silver and nanospheres for gold, favored by surface-tension gradients between laser irradiated and unirradiated regions. These metallic nanostructures exhibit excellent surface-enhanced Raman spectroscopy performance in trace detection of Rhodamine 6G (R6G), 4-mercaptobenzoic acid (4-MBA), and mercapto-5-nitrobenzimidazole molecules with high sensitivity (down to 10 ⁻¹² mol L ⁻¹ , 30 × 10 ⁻¹⁵ m for R6G), good reproducibility (relative standard deviation < 7%), and good dual-analyte detection ability with mixture ratios of R6G to 4-MBA ranging from 20 to 0.025. The conceptual importance of this plasma-enhanced-photochemical process may provide exciting opportunities in photochemical reactions, plasmofluidics, and material synthesis.